3-(n-carbamyloximino)-saturated thioheterocyclic compounds

ABSTRACT

PESTICIDALLY ACTIVE 3-(CARBAMYL- AND N-SUBSTITUTED-CARBAMYLOXIMINO)-SATURATED HETEROCYCLIC COMPOUNDS HAVE BEEN PREPARED. THESE COMPOUNDS ARE USEFUL IN COMBATING UNDESIRABLE PESTS SUCH AS INSECTS, ACARIDS, NEMATODES, VIRUSES, AND THE LIKE.

United States Patent 3,755,364 3-(N-CARBAMYLOXIMINO)-SATURATEDTHIOHETEROCYCLIC COMPOUNDS Thomas A. Magee, Mentor, Ohio, assignor toDiamond Shamrock Corporation, Cleveland, Ohio No Drawing.Continuation-impart of application Ser. No. 28,097, Apr. 13, 1970, whichis a continuation-impart of application Ser. No. 839,641, July 7, 1969,now abandoned. This application Feb. 2, 1972, Ser. No.

Int. Cl. C07 d 63/04, 65/04 US. Cl. 260-327 TH 12 Claims ABSTRACT OF THEDISCLOSURE Pesticidally active 3- (carbamylandN-substituted-carbamyloximino)-saturated heterocyclic compounds havebeen prepared. These compounds are useful in combating undesirable pestssuch as insects, acarids, nematodes, viruses, and the like.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of my copending application, Ser. No. 28,097,Thomas A. Magee, filed Apr. 13, 1970, which in turn is acontinuation-in-part of my copending application, 'Ser. No. 839,641,Thomas A. Magee, filed July 7, 1969, both now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention (2) Descriptionof the prior art The first synthetic carbamate insecticides werereported around 1947. The alcohol precursor in many of these carbamateshas been a substituted phenol, a naphthol or a heterocyclic hydroxycompound. More recently N-alkylcarbamates of oximes and thiohydroxamicacid esters have been reported.

US. Pat. 3,223,585 presents substituted carbamic acid esters of oximesof cyclic ketosulfides and substituted carbamic acid esters of cyclicthiohydroxamic acid esters of the following respective structures:

R1 R Ra\R4 R1 R2 0 R RWLS O R i 3 9 s gmtg 0) NOtN l l 10 4 1: 10 R5 R5R7 R3 I R5 R5 R7 R8 where R to R inclusive are substituents selectedfrom the group consisting of hydrogen and lower alkyl; n is an integerof 0 to 1; R represents a substituent selected from the group consistingof hydrogen and lower alkyl and R stands for lower alkyl. In thesecompounds the sulfur and the carbonyl carbon are in a 1,2 or a 1,4relationship; that is, they are separated by none or by two carbon3,755,364 Patented Aug. 28, 1973 atoms. In view of the apparentcorrelation of structure to pesticidal activity of the alkylcarbamatesand the reported activity of these cyclic compounds containing thesulfur and the carbamyl group in a 1,2 or a 1,4 relationship shown inthis patent, one would not predict compounds containing these groups inother than such a 1,2 or 1,4 relationship to exhibit high pesticidalactivity. We have now found, surprisingly, that N-alkylcarbamates ofoximes of cyclic ketosulfides in which the sulfur and the carbamylcarbon are in a 1,3 relationship, that is, they are separated by onecarbon atom, exhibit outstanding activity as insecticides, acaricidesand nematocides when utilized by contact or when utilized systemically.We have also found that N-alkylcarbamates of oximes of cyclicketo-oxides in which the oxygen and the carbamyl carbon are in a similar1,3-relationship, exhibit high pesticidal activity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS where X is --O,

n is an integer of 0, 1 or 2; m is an integer of 0 or 1; R through R canbe hydrogen, lower alkyl, lower thioalkoxy, and lower carboalkoxy withthe provision that any two of R through R on the same ring carbon atommay be connected to form a cyclohexyl or cyclohexenyl ring; and R and Rare hydrogen, lower alkyl or allyl. The term lower alkyl is used in itsaccepted chemical meaning of a carbon chain of from 1 to 6 carbon atoms.Also included are novel, pesticidally active intermediates listed asfollows: 2,4,4-trimethyltetrahydrothiophen-3-one; 2,2-dirnethyl 3carbethoxytetrahydrothiophen-4-one and2,2-dimethyltetrahydrothiophen-4-one.

It has been found that carbamates of oximes of 5- and 6-membered cyclicketosulfides hearing this 1,3-relationship of the sulphur to the ketogroup possess outstanding insecticidal, acaricidal, miticidal, and insome cases nematocidal activity. In these compounds, there is only onecarbon position between the sulfur position and the oxime carbonposition.

CHEMICAL COMPOUNDS-NAMES AND STRUCTURES Representative of the novel,pesticidally active compounds within the teaching of the foregoinggeneral structure are:

3-rnethylcarbamyloximinotetrahydrothiophene O I] UNO CNHCH:

3,3-dimethyl-4-methylcarbamyloximinotetrahydrofuran =NO CNHCHa H203-methyl-3-methylthio-4-methylcarbamyloximinotetrahydrofuran son, fi

=NOCNHCH3 H30 3-methylcarbamyloximinotetrahydrothiapyran l-oxide3-methylcarbamyloximino-4,4-dimethyltetrahydrothiapyran XNOENHCHa U 0 ND3NHCH L 3-methylcarbamy1oxirnin04,4-dimethyltetrahydrothiapyran 1,l-dioxide H3O CH3 T? No CNHCH:

3,3-dimethy1-4-allylcarbamyloximinotetrahydrothiophene H30 CH;

O TNO C INHCH CH=CHg CH S4-methyl-3-methylcarbamyloximinotetrahydrothiophene CH; O

I UNO'ONHCH;

6 4-methy1-3-methylcarbamyloximinotetrahydrothiapyran II NOCNHCH:

3-allylcarbamyloximino-4-methyltetrahydrothiapyran S3-carbamyloximino-4-methyltetrahydrothiapyran II NOONH,

s 4-methy1-3-methylcarbamyloximinotetrahydrothiapyranl-oxide l *NOaNHcHa Z-methyl-3-methylcarbamyloximinotetrahydrothiapyran 0 ll -NONHCH:

s -CHa 2,2-dimethyl-3-carbethoxytetrahydrothiophen-4-one CzH5-O2,2-dimethyltetrahydrothiophen-4-one H30- HaC 3 APPLICATION OF THECOMPOUNDS As used in this specification and claims, the terms pesticideand pesticidal are intended to refer to the killing and/or control ofinsects, nematodes, mites, organisms on plants, microorganisms, or thelike. Thus, it will be appreciated that applications commonly termednematocidal, insecticidal, miticidal, or the like are contemplated inthe employment of these terms.

While it is possible to apply the compounds of the present invention inundiluted form to the plant or other material to be protected, it isfrequently desirable to apply the novel N-alkylcarbamates in admixturewith either solid or liquid inert, pesticidal adjuvants. Thus, thesecompounds can be applied to the plants for pesticidal purposes, forexample, by spraying the plants with aqueous or organic solventdispersions of the compounds of this invention. The choice of anappropriate solvent is determined largely by the concentration of activeingredient which it is desired to employ, by the volatility required ina solvent, the cost of the solvent, and the nature of the material beingtreated. Among the many suitable solvents which can be employed ascarriers for the present pesticides, there may be mentioned hydrocarbonssuch as benzene, toluene, xylene, kerosene, diesel oil, fuel oil,petroleum, naphtha; ketones such as acetone, methyl ethyl ketone andcyclohexanone; chlorinated hydrocarbons such as carbon tetrachloride,chloroform, trichloroethylene, perchlorethylene; esters such as ethylacetate, amyl acetate and butyl acetate; the monoalkyl ethers ofethylene glycol, e.g., the monomethyl ethers; and the monoalkyl ethersof diethylene glycol, e.g., the monoethyl ether; alcohols such asethanol, isopropanol and amyl alcohol, etc.

The compounds of this invention can also be applied to plants and othermaterials along with inert solid adjuvants or carriers such as talc,pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, calciumcarbonate, bentonite, fullers earth, cottonseed hulls, wheat flour,soybean fiour, etc., pumice, tripoli, wood flour, walnut shell flour andlignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agentsare advantageously employed in both the solid and liquid compositions.The surface active agent can be anionic, cationic or nonionic incharacter. Typical classes of surface active agents include alkylsulfonates, alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates,alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols,ethylene oxide addition products of such esters; addition products oflong-chain mercaptans and ethylene oxide; sodium alkyl benzenesulfonates having 14 to 18 carbon atoms, alkylphenolethylene oxides,e.g., p-isooctyl phenol condensed with ethylene oxide units; and soaps,e.g., sodium stearate and sodium oleate.

The solid and liquid formulations can be prepared by any suitablemethod. Thus, the active ingredients, in finely divided form if a solid,may be tumbled together with a finely divided solid carrier.Alternatively, the active ingredient in liquid form, includingsolutions,.dispersions, emulsions, and suspensions thereof, may beadmixed with the solid carrier in finely divided form in amounts smallenough to preserve the free-flowing property of the final dustcompositions.

When solid compositions are employed, in order to obtain a high degreeof coverage with a minimum dosage of the formulation, it is desirablethat the formulation be in finely divided form. The dust containingactive ingredient usually should be sufiiciently fine that substantiallyall will pass through a ZO-mesh Tyler sieve. A dust which passes througha ZOO-mesh Tyler sieve also is satisfactory.

For dusting purposes, preferably formualtions are employed in which theactive ingredient is present in an amount of to 50 percent of the totalby weight. However, concentrations outside this range are operative andcompositions containing from 1 to 99 percent of active ingredient byweight are contemplated, the remainder being carrier and/or any otheradditive or adjuvant material which may be desired. It is oftenadvantageous to add small percentages of surface active agents, e.g.,0.5 to 1 percent of the total composition by weight, to dustformulations, such as the surface active agents previously set forth.

For spray application, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be in the form of a solution, suspension,dispersion or emulsion in aqueous or nonaqueous medium. Desirably, 0.5to 1.0 percent of a surface active agent, by weight, is included in theliquid composition.

Ifor adjuvant purposes, any desired quantity of surface actlve agent maybe employed, such as up to 250 percent of the active ingredient byweight. If the surface active agent is used only to impart wettingqualities, for example, to the spray solution, as little as 0.05percent, or less of the spray solution need be employed. The use oflarger amounts of surface active agent is not based upon wettingproperties but is a function of the physiological behavior of thesurface active agent. These considerations are particularly applicablein the case of the treatment of plants. In liquid formulations, theactive ingredient often constitutes not over 30 percent, by weight, ofthe total and may be 10 percent, or even as low as 0.01 percent.

For systemic use of the compounds of this invention, it is oftendesirable to apply the pesticide to the soil in the form of granules ofan inert material coated with or incorporating the active ingredient.The reasons for the use of such granules include elimination of waterduring application, reduction of drift, penetration through vegetativecoverage, easy handling, storage, and increased safety to handlers ofthe pesticides. Among frequently used granule carrier materials areattapulgite, montmorillonite, corn cobs, walnut shells, and expandedvermiculites. Depending on their physical properties, the toxicants areeither directly sprayed on the preformed granular base or are dissolvedin a suitable solvent and then sprayed onto the granular base afterwhich the solvent is removed by evaporation. The granule base materialsare usually 60 to 14 US. sieve size particles, although it will beappreciated that other size particles may also be employed.

PREPARATION OF DISCLOSED COMPOUNDS The compounds of the foregoinggeneral structure where one of R and R is hydrogen and the other is analkyl or allyl group may be synthesized (l) by the reaction of a loweralkyl or allyl isocyanate with the appropriate oxime precursor or (2) bythe reaction of the appropriate oxime precursor with phosgene followedby treatment of the resulting chloroformate intermediate with theappropriate primary amine to yield the desired compound of the foregoinggeneral structure. The compounds of the foregoing general structureWhere R and R are not hydrogen can be synthesized by (l) the reaction ofthe appropriate oxime with phosgene followed by treatment of theresulting chloroformate intermediate with the appropriate secondaryamine or (2) by reacting the oxime precursor with an appropriatecarbamyl halide to yield the desired compound of the foregoing generalstructure.

The oximes employed in the foregoing reactions are prepared from theircyclic ketone precursors by standard methods of reacting the ketone withhydroxylamine. The ketones are prepared by Dieckmann condensations or bypyrolysis of the barium salt of the appropriate aliphatic racr Broadly,the foregoing reactions can be characterized as a method for thepreparation of a composition of the structural formula:

(iii

Rz l ts H n is an integer of 0, 1 or 2; m is an integer of 0 or 1; R,through R can be hydrogen, lower alkyl, lower thioalkoxy, and lowercarboalkoxy with the provision that any two of R through R on the samering carbon atom may be connected to form a cyclohexyl or cyclohexenylring; and R and R are hydrogen, lower alkyl or allyl,

having the step of reacting (a) a compound selected from the structureof:

R7 Ra NOH with R through R X, n and m being the same as previouslystated, with (b) phosgene and (c) a primary or secondary amine with theorder of reaction of the three reactants varying with the specificcompound being synthesized.

In order that those skilled in the art may more completely understandthe present invention and the preferred methods by which the same may becarried into effect, the following specific examples may be offered:

EXAMPLE 1 Preparation of 3-methylcarbamyloximinotetrahydrothiophene Fiveg. (0.043 m.) of tetrahydrothiophen-S-one oxime whose preparation isreported in Helvetica Chimica Acta 27, 1285 (1944), is treated with 20ml. of methyl isocyanate. After the initial exothermic reaction hassubsided, the mixture was heated at reflux for hours, cooled, andstripped of volatiles to give 9.3 g. of an amber liquid residue of3-methylcarbamyloximinotetrahydrothiophene having a refractive index of11 1.5528 and the following elemental analysis. Calculated for C H N OS: C, 41.4%; H, 5.8%. Found: C, 41.8%; H, 5.8%.

EXAMPLE 2 Preparation of3-carbomethoxy-4-methylcarbamyloximinotetrahydrothiophene A mixture of5.3 g. (0.03 m.) of 3-carbomethoxytetrahydrothiophen-4-one oximeprepared according to the method described in the Journal of OrganicChemistry 18, 138 (1953), and 25 ml. of methyl isocyanate was heated atreflux for 5 hours and stripped of volatiles to give 8.5 g. of darkbrown viscous liquid of 3-carbomethoxy-4-methylcarbamyloximinotetrahydrothiophene with a foamy appearance asconfirmed by the infrared spectrum and the following elemental analysis.Calculated for C3H12N2O4SZ C, 41.4%; H, 5.2%. Found: C, 41.5%; H, 4.8%.

EXAMPLE 3 Preparation of2-carbomethoxy-3-methylcarbamyloximinotetrahydrothiophene This compoundis prepared in two steps starting with the use of2-carbomethoxytetrahydrothiophen-3-one.

A solution of 20 g. (0.125 m.) of 2-carbomethoxytetrahydrothiophen-3-oneand 20 g. (0.288 m.) of hydroxylamine hydrochloride in 300 ml. ofmethanol was treated with 22.9 g. (0.29 m.) of pyridine and heated underreflux for 16 hours. The residue after stripping of the solvent waspartitioned between ethyl acetate and water and the organic layer driedand stripped to give 14.3 g. of a dark brown liquid residue of2-carbomethoxytetrahydrothiophen-3-one oxime with the followingelemental analysis. Calculated for C H NO S: C, 41.1%; H, 5.2%. Found:C, 40.7%; H, 5.4%. Infrared analysis confirmed the assigned structure.

A solution of 5.3 g. (0.03 m.) of Z-carbomethoxytetrahydrothiophen-3-oneoxime and 25 ml. of methyl isocyanate (CH NCO) was heated under refluxfor 5 hours, then stripped of volatiles to give 9.0 g. of dark brown,

10 viscous liquid of Z-carbomethoxy 3methylcarbamyloximinotetrahydrothiophene as confirmed by the infraredspectrum.

EXAMPLE 4 Preparation of3,3-dimethyl-4-rnethylcarbamyloximinotetrahydrothiophene A solution of32.6 g. (0.25 m.) of 3,3-dirnethyltetrahydrothiophen-4-one, prepared asdescribed in the Joural of the Chemical Society, 650 (1961), 34.8 g.(0.5 m.) of hydroxylamine hydrochloride and 68 g. (0.5 m.) of sodiumacetate trihydrate in 200 ml. of ethanol and 100 ml. of water was heatedunder reflux for 4 hours. The volume was reduced on a rotary evaporatorand the residue partitioned between ethyl acetate and water. The ethylacetate solution Was washed with aqueous sodium bicar bonate, dried, andstripped to give 26 g. of pink solid of3,3-dimethyltetrahydrothiophen-4-one oxime, melting at 53-54 C. Theinfrared spectrum was consistent with the proposed structure.

A mixture of 14.5 g. (0.1 m.) of 3,3-dimethyltetrahydrothiophen-4-oneoxime, 7 m1. of methyl isocyanate, three drops of triethylamine and 50ml. of ether was heated under reflux for 3.5 hours and allowed to standovernight. Stripping of volatiles gave 20.7 g. of tan solid Whichinfrared analysis indicated to contain some starting material. This wasretreated with 7 ml. of methyl isocyanate, three drops of triethylamineand 50 ml. of ether for 3 hours. Stripping of volatiles gave 20 g. ofyellowtan solid of3,3-dimethyl-4-methylcarbamyloximinotetrahydrothiophene, melting at64-66 C. with the following elemental analysis. Calculated for C H N OS: N, 13.9%; S, 15.9%. Found: N, 14.2%; S, 15.2%. The infrared spectrumwas consistent with the assigned structure.

EXAMPLE 5 Preparation of3,3-dimethy1-4-allylcarbamyloximinotetrahydrothiophene A solution of 7.3g. (0.05 m.) of 3,3-dimethyltetrahydrothiophen-4-one oxime, 4.1 g. (0.05m.) of allyl isocyanate, 3 drops of triethylamine, and 100 ml. anhydrousether was heated under reflux for 16 hours and stripped of volatiles ona rotary evaporator to give 11.5 g. (100%) of viscous, yellow oil, n1.5276.

EXAMPLE 6 Preparation of 3,3-dimethyl-4-ethylcarbamyloximinotetrahydrothiophene A mixture of 7.3 g. (0.05 m.) of3,3-dimethyltetrahydrothiophen-4-one oxime, prepared by the proceduredescribed in Example 4, 3.9 g. (0.05 m.) of ethyl isocyanate, 3 drops oftriethylamine as the catalyst, and about 60 ml. of anhydrous ether washeated under reflux for 24 hours, cooled, and stripped on the rotaryevaporator. A white solid residue, 9.5 g., M.P. 9294 C. (which softenedat 87 C.), was obtained. This solid was 3,3-dimethyl-4-ethylcarbamyloximinotetrahydrothiophene, the desired product, asindicated by its infrared spectrum.

EXAMPLE 7 Preparation of4-methyl-3-*nethylcarbamyloximinotetrahydrothiophene To a 500 ml.,3-neck flask equipped with a condenser and heating mantle were added23.2 g. (0.2 m.) of 4-methyltetrahydrothiophen 3 one prepared asdescribed in Svensk Kemisk Tidskrift 57, 24 (1945), 172 ml. of 95%ethanol, 27.8 g. (0.4 m.) of hydroxylamine hydrochloride in 45 ml. ofwater, and 20.1 g. (0.19 m.) of anhydrous sodium carbonate in 45 ml. ofwater. The solution was heated at reflux for 6.5 hours, then stripped ofethanol through a rotary evaporator. The two-layer residue was extractedthree times with ethyl acetate. After being dried over anhydrousmagnesium sulfate, the solution was orange-tinted, white damp solid, theinfrared spectrum of which was in agreement with the desired structure,4-methyltetrahydrothiophen-3-one-oxime.

To a dried 200 ml. flask equipped with a condenser with drying tube andheating mantle were added 10.5 g. (0.08 m.) of4-methyl-3-ketotetrahydrothiophene oxime, 100 ml. of anhydrous ether, 5g. (0.088 m.) of methyl isocyanate and 4 drops of triethylamine. Thepale yellow solution was heated at reflux for 6 hours and then strippedthrough a rotary evaporator. There was collected 5.8 g. of amber viscousliquid which was dissolved in 50 m1. of anhydrous ether and treated with2.6 g. (0.046 m.) of methyl isocyanate and 3 drops of triethylamine. Thereaction mixture was heated at reflux for 24 hours and stripped througha rotary evaporator to give 6.2 g. of viscous amber liquid which was4-methyl-3-methylcarbamyloximinotetrahydrothiophene, as indicated by itsinfrared spectrum.

EXAMPLE 8 Preparation of2,2-dimethyl-4-methylcarbamyloximinotetrahydrothiophene To a suspensionof sodium ethoxide in benzene, prepared from 64 g. (1.5 m.) of 56.2%sodium hydride dispersion, 69 g. (1.5 m.) of absolute ethanol and 300ml. of benzene, was added over 20 minutes at or near reflux, .162 g.(1.35 m.) of ethyl Z-mercaptoacetate in 100 ml. of benzene. Theresulting slurry was treated over 25 ruinutes with a solution of 179 g.(1.4 m.) of ethyl 3,3-dimethylacrylate in 50 ml. of benzene and thenheated under reflux for 1.25 hours. The brown reaction mixture wasextracted with four portions of ice water. The combined aqueous extractswere immediately acidified with cold, concentrated HCl and extractedwith three portions of benzene. Distillation of the dried benzene layergave 198 g. of a yellow liquid,2,2-dimethyl-3-carbethoxytetrahydrothiophen-4-one, in three cuts havingrefractive indices of 11 1.4850 to 1.4874, and distilling at 69/0.08 mm.to 77/0.55 mm. The infrared spectra were consistent with the proposedstructure.

A mixture of 151.7 g. (0.75 m.) of 2,2-dimethyl-3-carbethoxytetrahydrothiophen-4-one, 200 cc. of acetic acid, 105 cc. ofconcentrated sulfuric acid and 750 cc. of water was stirred and heatedunder reflux for 8 hours. The mixture was cooled, extracted with twoportions of benzene, and the benzene extract washed with aqueous causticand dried over anhydrous magnesium sulfate. The filtered solution wasstripped and distilled through a 1 inch x 6 inch Vigreux column to give79 g. of colorless liquid, 2,2-dimethyltetrahydrothiophen-4-one, in twocuts with refractive indices n 1.4926 to 1.4929. The infrared spectrumwas consistent with the assigned structure.

A solution of 32.6 g. (0.25 m.) of 2,2-dimethyltetrahydrotlu'open-4-one,34.8 g. (0.5 m.) of hydroxylamine hydrochloride and 68 g. (0.5 m.) ofsodium acetate trihydrate in 200 ml. of 95 ethanol and 110 ml. of waterwas heated under reflux for 6 hours. The volume was reduced bydistillation at reduced pressure, and the residue was partitionedbetween ethyl acetate and water. The ethyl acetate layer was washed withaqueous sodium bicarbonate, dried and stripped to give 33.5 g. of aclear, orange-red liquid of 2-2-dimethyltetrahydrothiophen-4- one oximehaving a refractive index n 1.5292. The asigned structure was supportedby the infrared spectrum.

A solution of 14.5 g. (0.1 m.) of 2,2-dimethyltetrahydrothiophen-4-oneoxime, 10 ml. of methyl isocyanate and 60 ml. of benzene was treatedwith three drops of triethylamine. An exothermic reaction occurred afterwhich the reaction mixture was heated under reflux for 5 hours andstripped on a rotary evaporator to give 23 g. of a dark, red-brownviscous fluid, 2,2-dimethyl-4-methylcarbamyloximinotetrahydrothiophene.The infrared spectrum was consistent with the assigned structure.

12 EXAMPLE 9 Preparation of2,4,4-trimethyl-3-methylcarbamyloximinotetrahydrothiophene The2,4,4-trimethy1tetrahydrothiopherr-3-one oxime was prepared from asolution of 2 1.6 g. (0.15 m.) of 2,4,4-

trimethyltetrahydrothiophen-El-one, whose preparation is described inthe Journal of the Chemical Society 650 (1961), 20.9 g. (0.3 m.) ofhydroxylamine hydrochloride and 24.6 g. (0.3 m.) of sodium acetatetrihydrate in 200 ml. of ethanol and ml. of water which was heated underreflux for 4 hours and stripped on the rotary evaporator to give a whiteslurry which was filtered, Washed with water, and dried in a vacuumdesiccator over sodium hydroxide to give 19.5 g. of a white solidmelting at 81-83 C. The infrared spectrum was consistent with theproposed structure.

A solution of 9.6 g. (0.06 m.) of2,4,4-trimethyltetrahydrothiophen-3-one oxime, 5 ml. of methylisocyanate, and four drops of triethylamine in ml. of ether was heatedunder reflux for 6 hours, allowed to stand and stripped on the rotaryevaporator to give 12.5 g. of a cloudy liquid which became a pasty solidon standing. This compound was identified by its infrared spectrum as2,4,4 trimethyl 3 methylcarbamyloximinotetrahydrothiophene melting at7376 C.

EXAMPLE 10 Preparation of2,4,4-trimethyl-3-allylcarbamyloximinotetrahydrothiophene A solution of4.0 g. (0.025 m.) of 2,4,4-trimethyltetrahydrothiophen-3-one oxime,prepared as described in Example 9, 2 g. (0.025 m.) of allyl isocyanate,3 drops of triethylamine and 40 ml. of anhydrous ethyl ether was heatedfor 5.5 hours under reflux, then stripped by means of a rotaryevaporator to give 6.0 g. (100%) clear yellow oil 11 1.5242. Theinfrared spectrum was consistent with the assigned structure.

EXAMPLE 11 Preparation of3-ethyl-3-methyl-4-methylcarbamyloxirninotetrahydrothiophene Solutionsof (1) 132 g. (0.68 m.) of 2-bromomethyl-2- methylbutyric acid, whosepreparation is described in French Patent 1,231,163, in 350 ml. of 95%ethanol and 980 ml. of water and (2) 28 g. (0.7 m.) of sodium hydroxidein 265 ml. of water were added over two hours to a solution of 69 g.(0.75 m.) of mercaptoacetic acid in 400 ml. of water containing 66 g. ofsodium hydroxide at a rate such that two parts of solution 1) were addedfor each part of solution (2). For 45 minutes, the addition wasconducted at ambient temperature and the remainder of the time underreflux conditions. The resulting mixture was heated under reflux for 6hours, left overnight, stripped of the ethanol and the residue pouredonto ice and hydrochloric acid. The acid mixture was extracted with fourportions of ether which were combined, and the combination was extractedwith four portions of 10% aqueous sodium carbonate. Acidification of thecarbonate solution followed by extraction with ether, drying andstripping gave 79 g. of light yellow viscous liquid whose infraredspectrum was consistent with the assigned structure of 2-ethyl-2methyl-4-thiaadipic acid.

A mixture of 79 g. (0.38 m.) of 2-ethyl-2-methyl-4-thiaadipic acid and3.0 g. of barium hydroxide was added to a 100 ml., three-necked flaskequipped with a mechanical stirrer, thermometer, distilling head,condenser and receiving flask. The stirred mixture was heated in a Woodsmetal bath at a 200-310 C. bath temperature until dis tillation wascomplete. The organic layer was separated from the water layer with theaid of ether. The ether solution was dried over magnesium sulfate,filtered, and stripped. The residue was distilled through a 5 inch x /8inch Vigreux column and Claisen head with the following fractions of3ethyl-3-methyltetrahydrothiophen-4-one being collected after a smallforerun:

Cut No. 1: B.P. 81.5/9 mm., 5.5 g. yellow liquid,

Out No. 2: B.P. =80-8l.5/9.9 mm., 5.5 g. yellow liquid,

Cut No. 3: B.P. 81.5 /9.5 mm., 3.0 g. near-colorless liquid, n =1.4975

The proposed structure was supported by the infrared spectra.

A solution of 28.0 g. (0.2 m.) of3-ethyl-3-methyltetrahydrothiophen-4-one in 172 ml. of 95% ethanol, 27.8g. (0.4 m.) of hydroxylamine hydrochloride in 45 ml. of water, and 21.2g. (0.2 m.) of sodium carbonate in 45 ml. of water was heated in a 500ml. flask at reflux for 6 hours. The clear light yellow solution wasstripped of ethanol by means of rotary evaporator at water aspiratorpressure. The resulting two-layered residue was taken up in ethylacetate and the dried organic layer stripped to give 29.5 g. of amber,somewhat viscous liquid having a refractive index of n 1.5290. Theinfrared spectrum was consistent with the proposed structure of3-ethyl-3-methyltetrahydrothiophen-4-one oxime.

A solution of 11.2 g. (0.07 m.) of3-ethyl-3-methyltetrahydrothiophen-4-one oxime, 50 ml. of anhydrousether, 4.4 g. (0.077 m.) of methyl isocyanate and 4 drops oftriethylamine was charged to a dried 100 ml. flask equipped with acondenser with drying tube. The solution was heated at reflux for 6hours, then stripped by means of a rotary evaporator at reduced pressureto give 14.7 g. of an amber viscous liquid of3-ethyl-3-methyl-4-methylcarbamyloximinotetrahydrothiophene ofrefractive index n 1.5282. The infrared spectrum was consistent with theproposed structure.

EXAMPLE 12 Preparation of3,3-diethy1-4-methyl-carbamyloximinotetrahydrothiophene To a solution of42.4 grams (0.6 m.) of sodium carbonate in 450 ml. of water was added160 g. (0.77 m.) of 2-bromomethyl-Z-ethylbutyric acid, whose preparationis described in French Patent 1,231,163. A water insoluble upper layerformed. This mixture was added to a solution of 78.3 g. (0.85 m.) ofmercaptoacetic acid in 175 ml. of water containing 52.2 g. of potassiumhydroxide. The resulting mixture was stirred and heated under reflux for13.5 hours, cooled, and poured onto ice and hydrochloric acid. The etherextract of this mixture was in turn extracted with saturated aqueoussodium bicarbonate. Acidification of the basic solution followed byextraction with ether, drying, and stripping gave 68 g. of nearlycolorless viscous liquid whose infrared spectrum was compatible with theassigned structure of 2,2-diethyl-4-thiaadipic acid.

A mixture of 67 g. (0.3 m.) of 2,2-diethyl-4-thiaadipic acid and 2.1 g.of barium hydroxide in a simple distillation apparatus was heated with aWoods metal bath at 220-240 C. pot temperature until distillationceased. The water layer (4.5 g.) was separated from the distillate (33.9g.) and the dried organic layer distilled to give 11.4 g. of distillatein two cuts, B.P. 9397/7.39 mm., with refractive indices of n 1.4965 ton 1.4994. The infrared spectra were consistent with the assignedstructure of 3,3-diethyltetrahydrothiophen-4-one.

A solution of 11.0 g. (0.07 m.) of 3,3-diethyltetrahydrothiophen-4-onein 60 ml. of 95% ethanol, 9.8 g. (0.14 m.) of hydroxylaminehydrochloride in 15 ml. of water and 7.4 g. (0.07 m.) of sodiumcarbonate in 16 ml. of water were charged into a 200 ml. single-neckedflask equipped with a condenser and heating mantle. After being heatedat reflux for 15.5 hours, the clear yellow solution was stripped ofethanol through a rotary evaporator at aspirator pressure and theresidue suction filtered. The yellow 14 solids were dried in a vacuumdesiccator over Drieriteto give 10.4 g. of yellow solids melting at69-75 C. The mfrared spectrum was consistent with the proposed structureof 3,3-diethyltetrahydrothiophen-4-one oxime.

A solution of 7 g. (0.04 m.) of 3,3-diethyltetrahydrothiophen-4-oneoxime, 50 ml. of anhydrous ether, 2.5 g. (0.044 m.) of methyl isocyanateand 4 drops of triethylamine was charged to a dried ml. flask equippedwith a condenser with drying tube and heated with an oil bath at refluxtemperature for 6 hours. This mixture was stripped through a rotaryevaporator at reduced pressure to give 8.5 g. of light amber viscousliquid having a refractive index of n 1.5252. The infrared spectrum ofthe resulting liquid was consistent with its proposed structure of3,3-diethyl-4-methylcarbamyloximinotetrahydrothiophene.

EXAMPLE 13 Preparation of3-methyl-3-methylthio-4-methylcarbamyloximinotetrahydrothiophene To acooled, stirred solution of 131 g. (1.3 m.) of methyl methacrylate in400 ml. of anhydrous ether was added, over one hour at 05 C., 108.7 g.(1.3 m.) of methanesulfenyl chloride in 330 ml. of anhydrous ether. Theresulting solution was stirred at 05 C. for an additional hour, strippedof solvent and distilled through a 1" x 7" Vigreux column to give 186 g.(83%) of pale yellow liquid in two cuts, B.P. 76-77/ 5.3-5.5 mm., n1.4850 and B.P. 7677/5.15.3 mm., n 1.4850. The infrared spectrum wasconsistent with the proposed structure of methyl3-chloro-2-methyl-2-methylthiopropionate.

To a solution of sodium methoxide prepared from 16.1 g. (0.7 m.) ofsodium and 600 m1. of anhydrous meth anol was added 74.3 g. (0.7 m.) ofmethyl thioglycolate, a trace of sodium iodide and 128 g. (0.7 m.) ofmethyl 3- chloro-2-methyl-2-methylthiopropionate. The entire operationwas carried out under an atmosphere of nitrogen. After being heated atreflux for 4 hours, the reaction mixture was filtered and the filtratestripped of methanol under reduced pressure. A chloroform solution ofthe residue was washed with Water, dried and stripped of solvent to give123 g. (70%) of amber liquid 12 1.4963 whose infrared spectrum was inagreement with the proposed structure of dimethylZ-methyl-2-methylthio-4-thiaadipate.

To a slurry of sodium methoxide prepared from 16.6 g. (0.52 m.) ofmethanol, 22.3 g. (0.52 m.) of 56.2% sodium hydride dispersion and 1100ml. of anhydrous toluene was added a solution of 118.5 g. (0.47 m.) ofdimethyl 2-methyl-2-methylthio-4-thiaadipate in 200 m1. of toluene over30 minutes at 37-42 C. The resulting mixture was heated at 48-52 C. for5 hours, cooled and poured onto a mixture of ice and hydrochloric acid.The organic layer was combined with the ether extract of the aqueousportion, dried, stripped of solvent and distilled to give 52 g. (50%) ofyellow liquid in four cuts, B.P. 70-82/0.9 1pm., n 15009-15035. Theinfrared spectrum was consistent with the assigned structure of2-carbomethoxy-4- methyl-4-methylthiotetrahydrothiophen-3-one.

A stirred mixture of 48 g. (0.22 m.) of 2-carbomethoxy-4-methyl-4-rnethylthiotetrahydrothiophen-3-one and 384 ml. of 10%aqueous sulfuric acid was heated at reflux for 4 hours. The etherextract of the reaction mixture was dried, stripped of solvent anddistilled to give 21 g. (43%) of colorless to yellow liquid, B.P. 70/9.1mm., n 1.5080. The infrared spectrum was consistent with the assignedstructure of 3-methyl-3-methylthiotetrahydrothiophen-4-one.

A solution of 11.7 g. (0.072 In.) of3-methyl-3-methylthiotetrahydrothiophen-4-one, 10 g. (0.14 m.) ofhydroxylamine hydrochloride, and 7.6 g. (0.072 m.) of sodium carbonatein 62 ml. of ethanol and 32 ml. of water was heated at reflux for 5.5hours and stripped of solvent. An ethyl acetate solution of the residuewas washed with water, dried and stripped to give 12.2 g. of dark brown15 solid which melted around 40-50 C. The infrared spectrum wasconsistent with the proposed structure ofB-methyl-3methylthiotetrahydrothiopheni-one oxime.

To a dried 100 ml., l-neck flask equipped with a condenser, drying tubeand heating mantle were added 5.3 g. (0.03 m.) of3-methyl-3methylthiotetrahydrothiophen- 4-one oxime, 50 ml. of anhydrousether, 1.9 g. (0.033 m.) of methyl isocyanate and 3 drops oftriethylamine as a. catalyst. The mixture was heated at reflux for 6hours, then stripped through a rotary evaporator at reduced pressure togive 7.6 g. of dark amber, very viscous liquid, 3-methyl-3-methylthio 4methylcarbamyloximinotetrahydrothiophene, the desired product. Theinfrared spectrum was consistent with the structure.

EXAMPLE 14 Preparation of 3methylcarbamyloximinotetrahydrothiapyran Asolution of 7.9 g. (0.06 m.) of tetrahydro-3-thiapyrone oxime, preparedas described in the Journal of the American Chemical Society 74, 917(1952), ml. of methyl isocyanate, 3 drops of triethylamine and 50 ml. ofanhydrous ether was heated under reflux for 3 hours, left overnight, andstripped of volatiles on the rotary evaporator to give 12.5 g. ofyellow, viscous, cloudy liquid having a refractive index 11 1.5495. Theinfrared spectrum was consistent with the assigned structure.

EXAMPLE 15 Preparation of4,4-dimethyl-3methylcarbamyloximinotetrahydrothiapyran To a solution of14.4 g. (0.1 m.) of 4,4-dirnethyltetrahydrothiapyran-S-one, prepared bythe procedure described in Tetrahedron, 22, 285 (1966), in 100 ml. of95% ethanol, was added a solution of 14 g. (0.2 m.) of hydroxylaminehydrochloride in 35 m1. of water followed by a solution of 10.6 g. (0.1m.) of sodium carbonate in 35 ml. of water. A white solid, which was4,4-dimethyltetrahydrothiapyran-3-one oxime, separated immediately. Thiswas filtered, washed thoroughly with water, and air dried to give 12.5g. of white solid, MrP. 147-148 C. An additional 2.4 g. was recoveredfrom the filtrate, M.P. 145- 147 C. The infrared spectrum of the whitesolid indicated the absence of a group and the presence of OH andEXAMPLE 16 Preparation of3,3-dimethyl-4-methylcarbamyloximinotetrahyrofuran A solution of 6.9 g.(0.054 m.) of 3,3-dirnethyltetrahydrofuran-4-one oxirne, prepared asdescribed in Bulle- 16 tin de la Societe Chimique de France 1909 (1967),3.9 g. (0.068 m.) or" methyl isocyanate, 4 drops of triethylamine, and30 ml. of ahydrous ethyl ether was heated under reflux for 6 hours andstripped by means of a rotary evaporator to give 10 g. of colorlessviscous liquid, 11 1.4740, whose infrared spectrum was consistent withthe assigned structure.

EXAMPLE 17 Preparation of3allylcarbamyloximino4-rnethyltetrahydrothiapyran Anhydrous hydrogenbromide was bubbled through g. (1 m.) ofalpha-methyl-gamma-butyrolacetone until no further increase in weightwas observed. The dark liquid reaction mixture was dissolved inpetroleum ether. Volatile materials were removed by stripping underreduced pressure to obtain 184 g. of black liquid which was4-bromo-2-methylbutyric acid.

A solution of 91 g. (0.5 m.) of the above acid in 130 ml. of ethyl etherwas added to an ethereal solution of diazomethane at 0 C. After twohours reaction at 0 C., excess diazomethane was destroyed by treatmentwith acetic acid. The organic solution was washed with saturated aqueoussodium bicarbonate solution, then with water, dried over MgSO filtered,stripped of solvent and distilled to obtain 159 g. (81%) of greencolored liquid, methyl 4-bromo-2-methylbutyrate, B.P. 7273 C./7.98.9mm., 21 1.4545. Calcd. for C H BrO C, 36.9; H, 5.7. Found: C, 36.6; H,5.3.

A solution of the sodium salt of methyl thioglycolate prepared from 83.8g. (0.79 m.) of methyl thioglycolate, 18.2 g. (0.79 g. at.) of sodiumand 400 ml. of methanol was added over /2 hour to a solution of 153.5 g.(0.79 In.) of methyl 4-bromo-2-methylbutyrate in 400 ml. of methanol.The reaction mixture was heated at reflux for 40 minutes, cooled andpoured onto a mixture of ice and hydrochloric acid. The ether extract ofthis mixture was dried and distilled to obtain g. (66%) of dimethylZ-methyl- S-thiapimelate as a colorless liquid, B.P. 119-120 C./0.08-0.1 mm., n 1.4678. Calcd. for C H O S: C, 49.1; H, 7.3. Found: C,48.9; H, 7.3.

To an agitated slurry of 23 g. (0.55 m.) of 57% sodium hydride in 250ml. of refluxing benzene was added g. (0.5 m.) of dimethylZ-methyI-S-thiapimelate over a 40- minute period. The mixture was heatedat reflux for four hours, cooled, and poured onto an ice-hydrochloricacid mixture. The organic layer was separated, combined with a benzeneextract of the aqueous layer, dried and distilled. Obtained was 73.5 g.(78%) of 2-carbomethoxy-4-methyltetrahydrothiapyran-3-one as a colorlessliquid, B.P. 7 8- 82 C./ 0.3-0.4 mm., 11 1.5148. Calcd. for C H O S: C,51.0; H, 6.4. Found: C, 50.6; H, 6.5.

A mixture of 64 g. (0.34 m.) of 2-carbornethoxy-4-methyltetrahydrothiapyran-3-one, 234 g. of concentrated sulfuric acidand 1300 ml. of water was heated under reflux for 17 hours. The yellowsolution was saturated with sodium chloride and extracted with fiveportions of diethyl ether. The dried ether extracts were distilled toobtain 32.5 g. of 4-methyltetrahydrothiapyran-S-one as a colorlessliquid. B.P. 58 C./ l.3 mm., 11 1.513 9. Calcd. for C H OS: S, 24.6.Found: S, 24.5.

To a solution of 13 g. (0.1 m.) of 4-methyltetrahydrothiapyran-Zi-one in100 m1. of 95 ethanol was added a solution of 14 g. (0.02 m.) ofhydroxylamine hydrochloride in 35 ml. of water followed by a solution of10.6 g. (0.1 111.) of sodium carbonate in 35 ml. of water. The whitesolid precipitate was filtered off, washed with water, and dried toobtain 9.5 g. (60%) of 4-methyltetrahydrothiapyran-S-one oxime, M.P.112-113 C. Calcd. for C H NOS: C, 49.6; H, 7.6. Found: C, 49.1; H, 7.4.

A solution of 1.9 g. (0.013 m.) of 4-methyltetrahydrothiapyran-3-oneoxime, 1.1 g. (0.013 m.) of allyl isocyanate, and three drops oftriethylamine in 50 ml. of ether was heated at reflux for 4 hours. Thesolvent was stripped to obtain the desired product,3-allylcarbamyloximino-4-methyltetrahydrothiapyran, as a light yellowparaflin, M.P. 44-45 C. Calcd. for c,,H,,N,o,s,: C, 52.5; H, 7.1; N,12.4. Found: C, 51.8; H, 7.1; N, 12.0.

EXAMPLE 18 Preparation of4-methyl-3-methylcarbamyloximinotetrahydrothiapyran A solution of 4.4 g.(0.03 m.) of 4-methyltetrahydrothiapyran-3-one oxime prepared in Example17 above, 1.9 g. (0.033 m.) of methyl isocyanate, and four drops oftriethylamine in 100 ml. of ether was heated at reflux for 6.5 hours.The solvent was stripped to obtain the desired product,4-methyl-3-methylcarbamyloximino-tetrahydrothiapyran as a white solid,M.P. 59-60" C. Calcd. for C H N O S: C, 47.5; H, 7.0. Found: C, 47.5; H,6.9.

EXAMPLE 19 Preparation of4-methyl-3-methylcarbamyloximinotetrahydrothiapyran l-oxide A mixture of11 g. (0.051 m.) of sodium periodate, 60 ml. of water and 40 ml. ofmethanol was stirred at C. as 9.3 g. (0.046 m.) of4-methyl-3-methylcarbamyl oximinotetrahydrothiapyran (product of Example18 above) was added. The mixture was stirred overnight at 0 C., allowedto warm to 12 C., and filtered. The filtrate was extracted withchloroform. Stripping of the dried chloroform extract gave 7.9 g. ofwhite solid, M.P. 134-138 C. which was recrystallized fromethanol-petroleum ether to give 3.8 g. of the desired product, 4- methyl3-methylcarbamyloximinotetrahydrothiapyran 1- oxide, as a white solid,M.P. ISO-152 C. Calcd. for C H N O S: C, 44.0; H, 6.5. Found: C, 44.1;H, 6.8.

EXAMPLE 20 Preparation of 3-carbamyloximino- 4-methyltetrahydrothiapyranA chilled solution of 0.033 m. of phosgene in 50 ml. of diethyl etherwas treated first with 0.03 m. of N,N-dimethylaniline, then with asolution of 4.4 g. (0.03 m.) of 4-methyltetrahydrothiapyran-3-one oxime(prepared as described in Example 17). After being stirred for about onehour, the mixture was treated with 6 ml. of 29% aqueous ammonia. Thesolid which separated was filtered ofl, washed with water and dried.3-carbamyloximino-4-methyltetrahydrothiapyran, the desired product, wasobtained as a white solid, M.P. 146-147 C. Calcd. for C'7H12N2O2S: C,44.6; H, 6.4; N, 14.9. Found: C, 44.3; H, 6.3; N, 14.8.

EXAMPLE 21 Preparation of2-methyl-3-methylcarbamyloximinotetrahydrothiapyran To a solution of13.6 g. (0.59 m.) of sodium in 360 ml. of methanol was added in thefollowing order: 71.5 g. (0.59 m.) of methyl 2-mercaptoproprionate, atrace of sodium iodide, and 80.6 g. (0.59 m.) of methyl4-chlorobutyrate. The mixture was heated at reflux for three hours,cooled and filtered. The filtrate was distilled to give 92 g. ofdimethyl 2-methyl-3-thiapimelate as a colorless liquid, B.P. 109 C./0.7mm., 11 1.4664. Calcd. for C H O S: C, 49.1; H, 7.3. Found: C, 49.2; H,7.2.

To an agitated slurry of 18.1 g. (0.43 m.) of 57% sodium hydrideemulsion in 275 ml. of refluxing benzene was added, over one hour, 82 g.(0.39 m.) of dimethyl 2-methyl-3-thiapimelate. Two ml. of ethanol wereadded to initiate a reaction. The mixture was then heated under refluxfor four hours, cooled, and poured onto an icehydrochloric acid mixture.The organic layer was sepa- 18 rated and combined with a benzene extractof the aqueous layer. Stripping of solvents gave a residue of 61.2 g. of2-carbomethoxy-2-methyltetrahydrothiapyran-3-one as a tan solid, M.P.-81 C. Calcd. for C H OS: C, 51.0; H, 6.4. Found: C, 51.1; H, 6.4.

A solution of 57.5 g. (0.3 m.) of 2-carbomethoxy-2-methyltetrahydrothiapyran-3-one, 206 g. of concentrated sulfuric acid,and 1015 ml. of water was heated at reflux for 16.5 hours. The cooledmixture was extracted with ten portions of diethyl ether. Distillationof the ether extracts gave 27 g. of colorless liquid,2-methyltetrahydrothiapyran-3-one, B.P. 66 C./2.1 mm., n 1.5116. Calcd.for C H OS: C, 55.4; H, 7.7. Found: C, 55.3; H, 7.6.

A solution of 23.5 g. (0.18 m.) of 2-methyltetrahydrothiapyran-B-one, 25g. (0.36 m.) of hydroxylamine hydrochloride, and 19.1 g. (0.18 m.) ofsodium carbonate in -180 ml. of ethanol and 126 ml. of water was heatedunder reflux for 21 hours. Removal of the alcohol gave a slurry whichwas filtered to give 24.2 g. (93%) of beige colored solid, M.P. 88-89 C.Recrystallization from ethanol-water yieldedZ-methyltetrahydrothiapyran- 3-one oxime as a white solid, M.P. 1101llC. Calcd. for C H NOS: C, 49.6; H, 7.6. Found: C, 49.3; H, 7.5.

A solution of 5.8 g. (0.04 m.) of Z-methyltetrahydrothiapyran-3-oneoxime, 2.5 g. (0.044 m.) of methyl isocyanate and three drops oftriethylamine in 75 ml. of ether was refluxed for 16 hours. Removal ofsolvent gave 8.3 g. of tan solid, M.P. l01103 C., which is the desiredproduct, 2 methyl-3-methylcarbamyloximinotetrahydrothiapyran. Calcd. forC H N O S: C, 47.5; H, 7.0; N, 13.9. Found: C, 47.1; H, 6.9; N, 14.4.

UTILITY OF THE DISCLOSED COMPOUNDS The following tests demonstrate theutility of the compounds of this invention in general for killing and/orcontrol of pests and in particular the control of insects, acarids,bacteria, viruses, nematodes, and the like.

EXAMPLE 22 Bean aphid spray and systemic test This test determines theinsecticidal activity of the compound being tested against the beanaphid Aphis fabae. Stock formulations containing 500 p.p.m. of each testchemical are prepared using 0.05 g. of the test chemical (or 0.05 ml. ifa liquid), 4.0 ml. acetone containing 0.25% (v./v.) Triton X-155, and96.0 ml. deionized water and are used in both soil drench and spraytreatments. The stock formulations are diluted to obtain the appropriatelower concentrations maintaining the concentration level of alladjuvants. The bean aphid is cultured on nasturtium plants var. TallSingle, no attempt being made to select insects of a given age in thesetests. Single nasturtium test plants growing in soil in individual 2%inch fiber pots are then infested with populations of to 200 aphids.

In the spray application, 50 ml. of the stock or diluted formulation isuniformly sprayed onto the plants. In the systemic application, 11.2 ml.of stock or diluted formulation is applied to the soil containing theplant. A dosage of 11.2 ml. of the formulation containing 500 p.p.m. oftest chemical is equivalent to a dosage of the test chemical of 16pounds per acre.

A piece of moisture resistant thermoplastic heat sealable film, 4" x 4"is slit to the center, fitted around the base of the stem of the testplant in a fashion such as to form a shallow inverted cone and crimpedin place. The pot-plant-film test units under fluorescent lights aregiven bottom watering for the duration of the test. Dead aphids fallonto the film where they can easily be counted. Percentage mortality isdetermined three days after treatment. Using this procedure, the resultsin Table 1 are obtained concentrations with each test chemical:

in the spray and systemic applications at the indicated TABLE 1"Compound tested 3-methylcarbamyloximinotetrahydrothiophene3-carbomethoxy-kmethyleorbamyloximinotetraiiydrothiophene:

3,3-dimethyl4-methylcarbamyloximinotetrahydrothiophene2,2-dimethylt-methylcarbamyloximinotetrahydrothiophene.S-Inethylcarbamyloximinotetrehydrothiapyran3,3-di1nethyl-4-allylca.rbamyloximinotetrahydrothiophene-3,3-dimethyl-tothylcarbamyloximinotetrahydrothiophene2,4,4-trimethyl-3-methylcarbamyloximinotetrahydrotlnophene-3,3-dimethyl-4-methylcarbamyloximinotetrahydrofuran3-methyI-S-methylthio-tmethylcarb amyloximinotetrahydrothiophene4-methy1-3methylcarbamyloximinotetrahydrothigphene4,4dimethyHi-methylcarbamyloximinotetrahydrothiapyrau2,4,4-trimethy1-3-al1ylcarbamyloximinotetrahydrothiophene.3-allylcarbamyloximino-4-methy1tetrahydrethiapyran-.-methyl-Zi-methylcarbamyloximinotetrahydrothiapyr4-methyl-S-methylcarhamyloximinotetrahydrothiapyran l-ox'ldecacarbamyloximino--methyltet-rahydrothiapyran.

2-methy1-3-methylcarbamyloximinotetrahydrothiapymn Spray applicationSystemic application Percent mortality at Percent mortality atconcentration in p.p.m. ot'- concentration in 1b .lacre ot EXAMPLE 23Bean aphid spray and systemic test-Residual activity This testdetermines the residual insecticidal activity of the compound beingtested against the bean aphid Aphis fabae. The test procedure describedin Example 22 above 25 of two Lima bean plants (var. Sieva) grown in ZA-inch pots.

The spray and systemic application methods described in Example 22 aboveare used to apply the test formulations to the infested plants and soil.After three days, two orthe four leaves treated are examined andmortality TABLE 2 Spray application Systemic application Concen- Percentmortality Goncen- Percent mortality tretion, tration, Compound testedp.p.m. 3 days 7 days lbs/acre 3 days 7 days 256 1003,3-dimethyl-4-methylcarbamyloxlminotetrehydrothiophene 2 32 100 16 83is followed with readings being made at 3 and at 7 days after spray andsoil applications of diluted formulations of the chemical. Results ofresidual insecticidal activity tests are shown in Table 2.

is determined. Should a compound be an effective miticide, the other twoleaves are available to obtain information on the residual activity ofthe formulation. Using this procedure, the results shown in Table 3 areobtained:

TABLE 3 Spray application Systemic application Percent mortality atPercent mortality at concentration in p.p.m. ofconcentration in lb/acreof- Compound tested 500 250 128 64 8 4 2 13-methylcarbamylmdminotetrahydrothiophene3,3-dimethyl-et-methylcarbarnyloximinotetrahydrothiophene----2,2-d1methyl--methylearbamyloximinotetrahydrothiophene3-methylcarbamyloximinotetrahydrothiapyran 1 Indicates inhibition offeeding.

EXAMPLE 24 Red spider mite spray and systemic test This test determinesthe acaricidal activity of the compound being tested against the redspider mite, Tetranychus sp. Stock formulations containing 500 p.p.m. ofeach test chemical are prepared by the procedure described in Example 22and are used in both the soil drench and spray treatment. The stockculture of mites is maintained on I EXAMPLE 25 Red spider mite spray andsystemic test-Residual activity This test determines the residualacaricidal activity of 'the compound being tested against the red spidermite, Tetranychus sp. The test procedure is the same as described inExample 24, except that readings are taken at three and at seven daysafter spray and soil applications of the diluted formulations of thechemical. Results of residual acaricidal activity tests are shown inTable 4 as follows:

TABLE 4 Spray application Systemic application Concen- Percent mortalityConcen- Percent mortality tration, tration, Compound tested p.p.m. 3days 7 days lbs/acre 3 days 7 days 64 100 893,3-dimethyl-4-methylcarbamyloximinotetrahydrothiophene.- 3 13% 8 99 7EXAMPLE 26 15 EXAMPLE 28 Red-banded leaf roller leaf spray test Redspider mite spray and systemic testDifferent strains This testdetermines the insecticidal activity of the This test determines the acac dal a iv y of the compound being tested against the red-banded leafroller,

pound being tested against the red spider mite, Tetrany-Argyrotaeniavelutinana, 611115 P-, one strain being Organophosphatel'eslstant and The test species is composed of newly hatched larvae an rStrain being OIgaBOPhOSPhate susceptible. of the red-banded leaf roller.Paired fully expanded pri- The test PICK?edure is that described inExample mary leaves excised from Pinto bean plants are mainexcept thatreadings are taken at three and at seven days mi d i aquapics (SyndicateSales, Inc., Kokomo, after p y and Soil applications of the di111td m l25 Indiana) and sprayed with 50 ml. of stock or diluted tions Of thechemical. Results Of these acaracldal activity formulation in aturntable pray hood. stock con. tests are shown in Table 5: tains 1000p.p.m. of each test chemical and is prepared TABLE 5 Spray applicationSystemic application Percent mortality Percent mortality Concenm Concen-Susceptible Resistant tration, tration, Compound t t d p.p.m. 3 days 3days lbs/acre 3 days 7 days 3 days 7 days 64 100 100 s 100 100 100 1008,3-dimethyl--methylcarbamyloximlnotetrahydrothiophene{ 16 9 3 g 12g 1 a11 43 8 EXAMPLE 27 using the procedure of Example 22 except the amountof chemical is 0.1 g. instead of 0.05 g. The stock formula- H fl spraytest tions are diluted in the same manner to obtain the appropriatelower concentrations.

This test determines the insecticidal activity of the g g gg gfig ggfijgfi fi fii ?;12inii i$3 compound being tested against adulthouseflies, Muscu P P P 0 water agar in a Petri dish. Ten newly hatchedred-banded leaf roller larvae are transferred to the leaf and the Petridish is covered. These are held at 72 F. for three days when mortalityis determined. Results of insecticidal acdomestica.

Stock formulations containing 500 p.p.m. of each test chemical areprepared using the procedure described in Example 22 above and arediluted to obtain the apfivity are given in Table propriate lowerconcentrations. TABLE 7 Ten adult flies are placed in a cylindricalscreen cage Percent mortality 1% by 4 inches fabricated from 20-meshstainless steel at concentration screening and are sprayed with 50 ml.of the stock or w t diluted formulation. The flies are supplied food anddrink Compound e e 1,000 500 250 from a dextrose solution by draping apaper wick over the ggif fiagigyiggfigmg{ 1 3385 3859 70 outside of thescreen cylinder and are able to feed and tetrahydrothiophene so 0 drinkad libitum. Percent mortality obtained is determined tgfifi ifgfiggggfifiili fffiflfffff 80 25 three days after treatment. Results of theseinsecticidal smethYlcarbamyhximmotetrahydmthiapwan 62 142,4,4-trimethyl-3-methylcarbarnyloximinoactivity tests are shown inTable 6: tetrahydrothiophene- 65 TABLE 6 Percent mortality atconcentration in p.p.m. oi-

3,3-dimethyl-4-ethylcarbamyloximinotetrahydrothiophene 1003-ethyl3-methyl+methylcarbamyloximinotetrahydrothiopheneS-methyl-S-methylthio-ekmethylcarbamyloximinotetrahydrothiophene4-rnethyl-3-methylcarbamyloximinotetrahydrothiophene 1002,4,4-trimethyl-3-methylcarbamyloximinotetrahydrothiophene4,4-dimethyl-3-methylcarbamyloximinotetrahydrothiapyran4-methyl-3-methylcarbamyloximinotetrahydrothiapyran2-methyl-S-methylcarbamyloximinotetrahydrothiapyran 23 24 EXAMPLE 29TABLE 9 Dosage Percent control Mexican bean beetle leaf spray testCompound lbs'lacre Mun. Bean Com 2,2-di th 14- th to This testdetermines the insecticidahactivity of the fi f g g compound beingtested against the Mexican bean be t thiophene 64 1,000 100 (Epilachncvar ivestis). The test procedure is the same as igfi gff g g f fggigggff64 100 that described in Example 28 with the exception that one-3-methyl-3-methylthiotetr day old larvae of the Mexican bean beetleinstead of leaf hydrothiophenmne 32 roller larvae are used. 10 E Thesetests are held at 72 F. for three days when EXAMPL mortality and feedinginhibition are determined. The feed- Root'knot i test ing inhibition isan indication of the repellent properties This te i n evalua ion of theeffectiveness of the of the test material. Results of insecticidalactivity are compounds of this invention against infection by root-knotgiven in Table 8: nematodes (Meloidogyne spp.).

TABLE 8 Percent mortality at concentration in p.p.rn. of-

Compound tested 1, 000 500 3-methylcarbamyioximinotetrahydrothionhene 1100 1 100 3-carbomethoxyt-methylcarbamyloximinotetrahydrothiophene 1 800 3,3-dimethy14-methylearbamyloximinotetrahydrothiophene-- l 1002,Z-Gimethy1-4-methylcarbamyloximinotetrahydrothiophene i 1003-methylcarbamyloximinotetrahydrothiapyran l 1003,3-dimethyl+ai1ylearbamyioximinotetrahydrothiophene3,3-d.imethyl-4-ethylcarbamyloximinotetrahydrothiophene2,4,4-trimethyl-3-methylcarbamyloximinotetrahydrqthioph2,4,i-trimethyl-B-allylcarbamyloximinotetrahydrotlnophene--3-ethyi-B-methyM-methylcarbamyloximinotetrahydro h3,3-dimethyl-4-methylcarbamyloximinotetrahydrofnmn3-methyl-8-methy1thio-4-methylcarbamyloximinotetrahydrothiophene l 100a-methyl-3-methylcarbamyloximinotetrahydrothiophene4,4-dimethyl-3-methylcarbamyloximinotetrahydrothiapyran-..4-methyl-3-methy1carbamyloximinotetrahydrothiapyrantelnethyl-3-methylcarbamyloximinotetrahydrothiapyran l-oxida3-carbamyloximin0-4.n:iethyletrahydrothiapyran2-methyl-B-methylcerbamyloximinotetrahydrothiapyran Indicates inhibitionof feeding.

EXAMPLE composted greenhouse soil, diluted by one-third with cleanwashed sand, is infested with about two grams of Vmcide test knotted orgalled tomato roots per pot. Treatment is accomplished by applying 25ml. of the formulated chemi- TeSt compounds exalllmed for ablhty 9control cal onto the infested soil. The formulation contains 0.056southern bean mosaic O P bean and malle dwarf g. of the test chemical,1.0 ml. stock emulsifier solution virus on Golden Bantam sweet corn.Stock formulations 5% Triton 55 in acetone by volume) 249 mL C t n ng1000 P-P- of each test compound are m deionized water giving aconcentration of 2240 p.p.m. pared usmg the procedurepf Example 22except that the Lower concentrations are achieved by dilution. amount ofchemical used s g- Instead Of and After treatment with the testchemical, the soil, inocare used in both the soil drcn and the fOllageSpray ulum, and chemical are thoroughly mixed, returned to thetreatments. Virus inoculation is made by the carborundum pot d hmixture, incubated for seven days at 20 C. leaf abraSiOumB 1 t0 P P totreatment and constant moisture. After incubation with the first In t efoliage p y appilcatlon, of the stock chemical in the table, twoseedlings of Rutgers tomato test form lati n at 1 90 new are umformlysprayed on transplants and three Windsor bean (Vicia faba) seeds i116 pf the S011 dfench treatmfimti the Stock test are set in each pot. Afterincubation with the remaining formulation is also applied at the soilsurface of each six chemicals in the table two s dl' pot prior to sprayat a dosage of the test chemical of 64 ee mgs of Rutgers to matetransplants and three garden nasturtium (Nasturti- Polmds P? acre 32Rounds P j Effective control um spp.) seeds are set in each pot. Rootsare removed is determined through visual observation of the presence f hsoil ft r three weeks of o th d r t d f r or absence of viral infectionsymptoms ten days after gall (root-knot nematode infection) formation.Windsor inoculation. Using this procedure, the results shown in beanroots or nasturtium are evaluated only when Table 9 are obtained:necrosis of the tomato host has occurred. A rating of in- TABLE 10Percent control at concentration in lbs/acre of- Compound tested 64 3216 8 4 2 1 z-methylcarbamyloximinotetrahydrothiophene 100 953,3-dimethyl-d-methylcarhamylomminotetrahydrothiophene 100 100 100 100100 90 50 3,3-dimethyl-4-ethy1carbamyloximinotetrahydrothiophene.. 100100 0 3,3-din ethyl-4a11y1carbamyloximjnotetrahydrothiophene. 100 40 402,4,4-trimethyl-3-methylcarbamyloxim1notetrahydrothiophene. 1G0 100 03-ethyl-3-methyl4-methylcarbamyloxlminotetrahydrothiophene 100 30 Ia-methy1-3-methylth o-4methylcarbamyloximinotetrahydr0thiophene.-. 10070 B0 -a1lyloarbamyloxinnno-4-methyltetrahydrothiapyran 100 e 51 35 "s54-111ethy1-3-methylcarbamyloidminotetrahydrothiapyran .z. 100 100 165100 37 4-methy1-3-methyicarbamyloximinotetrahydrothiapyran l-oxide 100100 100 97 3-carbamylox1mino-4-methyltetrahydrotlfiapyran l 1002-methyI-B-methylearbamyloximinotetrahydrothiapyran.; t u 100 fectionfrom to 10 is recorded: 0=no galls or complete control and 10=heavilygalled roots comparable to controls. Each of the root systems is ratedseparately and the average is multiplied by 10 and subtracted from 100to give percent nematode control. Results of the tests are shown inTable '10.

EXAMPLE 32 Greenhouse whitefiy test Young tomato plants in 3 /2-inchclay pots are treated by soil drench at the rate of chemical indicatedin the following test results and exposed to a heavy population ofwhitefly adults in the greenhouse for seven days. The plants are treatedby pouring the chemical formulation in a test solution on the soil atrates of 8 or less pounds per acre. Stock formulations containing 500p.p.m. of the test chemicals are prepared and diluted by the proceduredescribed in Example 22. After seven days, there was a high density ofeggs on the check plants and all plants were moved to a holding room.Fifteen days after treatment, the total number of live larvae on thethird and fourth leaves was determined and the percent controlcalculated. Results of this test are shown in Table 11:

TABLE 11 Concentration Percent Compound tested lbs/acre control3,3-dlmethyl--methylcarbamyloxlmlnotetrahyg 32 drothlophene 0 41 EXAMPLE33 B011 weevil test Adult boll weevil insects in cylindrical fly cages,of the type used in Example 27, were sprayed with a suspension of thetested chemical named below and later supplied sugar water using thestandard technique of placing the water to be available to feed theinsects. Mortality counts were made three days later. Stock formulationscontaining 500 ppm. of the test chemicals are prepared and diluted bythe procedure described in Example 22. Results of this test are shown inTable 12:

Test formulations are examined for ability to inhibit the colonialgrowth of Xanthomonas phaseoli (X.p.), at various concentrations. Thebasic test formulation contains 0.125 g. of the test chemical (or 0.125ml. if a liquid), 4.0 ml. stock emulsifier solution (0.25% Triton X- 155in acetone by volume) and 96.0 ml. deionized water, the concentration oftoxicant in this formulation being 1250 p.p.m. Lower concentrations oftoxicant are obtained by diluting the basic formulation with distilledwater.

Two ml. of the formulation is dispensed into a test tube which is thenplaced into a water bath maintained at 47 C. From a stock preparation(also held at 47 C), 8 ml. of Difco nutrient agar is added to the testtube giving a 1:5 dilution or a final concentration of 250 p.p.m.chemical in the agar. The contents of the test tube are then thoroughlymixed, while still warm, with the aid of a Vortex type mixer andimmediately poured into a sterile polystyrene Petri dish (100 x 15 mm.).After the agar in the plate is set, a suspension of the organism isstreaked TABLE 13 Concen- Percent tratlon, control, Compound p.p.m. X.p.

2,4,4-trtmethyltetrahydrothiophen-3-one oxime 128 502,2-dimethyltetrahydrothlophen-4-one 250 50 It is to be understood thatalthough the invention has been described with specific reference toparticular embodiments thereof, it is not to be so limited since changesand alterations therein may be made which are within the full intendedscope of this invention as defined in the appended claims.

What is claimed is:

1. A composition of matter of the structural formula n is an integer of0, l or 2; m is an integer of 0 or 1; R through R can be hydrogen, loweralkyl, lower thioalkoxy, and lower carboalkoxy with the provision thatany two of R, through R; on the same ring carbon atom may be connectedto form a cyclohexyl or cyclohexenyl ring; and R and R are hydrogen,lower alkyl or allyl.

2. A composition of matter of claim 1 wherein R or R are hydrogen orlower alkyl.

3. A composition of matter of claim 1 wherein R or R is allyl.

4. A composition of matter of the structural formula of claim 1 selectedfrom the group consisting of:3-methylcarbamyloximinotetrahydrothiophene;3-carbomethoxy-4-methylcarbamyloximinotetrahydrothiophene;Z-carbomethoxy-3-methylcarbamyloximinotetrahydrothiophene;3,3-dimethyl-4-methylcarbamyloximinotetrahydrothiophene;3,3-dimethyl-4-ethylcarbamyloximinotetrahydrothiophene;2,2-dimethyl-4-methylcarbamyloximinotetrahydrothiophene;2,4,4-trirnethyl-3-methylcarbamyloxirninotetrahydrothiophene;3-methylcarbamyloximinotetrahydrothiapyran;3-ethyl-3-methyl-4-methylcanbamyloximinotetrahydrothiophene;3,3-dimethyl-4-allylcarbamyloximinotetrahydrothiophene;2,4,4-trimethyl-3-allylcarbamyloximinotetrahydrothiophene;3-methyl-3-methylthio-4-methylcarbamyloximinotetrahydrothiophene;4-methyl-3-methylcarbamyloximinotetrahydrothiophene;4,4-dimethyl-3-methylcarbamyloximinotetrahydrothiapyran;4-methyl-3-methylcarbamyloximinotetrahydrothiapyran;

v I 27 4-methyl-3-methylcarbamyloximinotetrahydrothiapyran l-oxide;3-carbamy1oximino-4-methyltetrahydrothiapyran;Z-methyl-3-methylcarbamyloximinotetrahydrothiapyran; and I3-allylcarbamyloximino 4-methyltetrahydrothiapyran.

5. A composition of matter-of claim 1 wherein said comuposition is 3'methylcarbamyloximinotetrahydrothiophene.

6. A composition of matter ofclaim 1 wherein said composition-is 3,3dimethyl 4 methylcarbamyloximinotetrahydrothiophene.

'7QA composition of matter of claim 1 wherein said composition is'3-Inethylcarbamyloximinotetrahydrothiopyran.

8. A composition of matter of claim 1 wherein said composition is 4,4dimethyl',- '3 methylcarbamyloximinotetrahydrothiapyran.

9. A composition of matter of claim 1 wherein said composition is 3methyl 3 methylthio 4 methylcarbamyloximinotetrahydrothiophene.

10. A composition of matter of claim 1 wherein said 28 composition is 4methyl 3 methylcarbamyloximinotetrahydrothiophene.

11. A composition of matter of claim 1 wherein said composition is 4methyl 3 methylcarbamyloximinotetrahydrothiapyran.

12. A composition of matter of claim 1 wherein said composition is 3allylcarbamyloximino 4 methyltetrahydrothia-pyran.

References Cited UNITED STATES PATENTS 3,223,585 12/1965 Addor 167-33HENRY R. JILES, Primary Examiner C. M. S. JAISLE, Assistant Examiner US.Cl. X.R.

71-88, 90, 91, 94, 95; 260293.85, 293.86, 326.3, 329 AM, 332.1, 332.2 R,332.2 C, 332.3 R, 345.7, 347.2, 347.3, 481 R, 537 S; 424-267, 274, 275,283, 285

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,755,364 Dated 1 August 28, 1975 Inventor(s) Thomas A Magee It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Delete the double bond and substitute a single bond in the heterocyclicring moiety of each of the following structures:

' Col. 3, lines 69-75; Q

Col. A, lines 2-8; co1. 1iues 11-15;

Col. 4, lines 19-23; I Col. 4, lines 26-32.

Signed and sealed this 18th as of June 1971 (SEAL) Attest:

EDWARD H.FIETCHER,JR. c.v MARsHALL. 1mm Attesting Officer Commissionerof Patents F ORM PO-1050 (10-69) USCOMM-DC 603764 69 k U.ST GOVERNMENTPRINTING OFFICE: 1969 0-866-834

